Dinuclear Nickel-Ruthenium Complexes as Functional Bio-Inspired Models of [NiFe] Hydrogenases

Three new dinuclear nickel ruthenium complexes, namely [Ni(xbsms)Ru(p‐cymene)Cl]+, [Ni(emi)Ru(CO)2Cl2]2– and [Ni(emi)Ru(p‐cymene)Cl]– [H2xbsms = 1,2‐bis(4‐mercapto‐3,3‐dimethyl‐2‐thiabutyl)benzene, H2emi = N,N′‐ethylenebis(2‐mercaptoisobutyramide], have been synthesized and fully characterized as mo...

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Bibliographic Details
Published in:European Journal of Inorganic Chemistry 2007-06, Vol.2007 (18), p.2613-2626
Main Authors: Oudart, Yohan, Artero, Vincent, Pécaut, Jacques, Lebrun, Colette, Fontecave, Marc
Format: Article
Language:English
Subjects:
Biomimetic chemistry
Electrocatalysis
Hydrogen
Hydrogenases
Nickel
Ruthenium
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Summary:Three new dinuclear nickel ruthenium complexes, namely [Ni(xbsms)Ru(p‐cymene)Cl]+, [Ni(emi)Ru(CO)2Cl2]2– and [Ni(emi)Ru(p‐cymene)Cl]– [H2xbsms = 1,2‐bis(4‐mercapto‐3,3‐dimethyl‐2‐thiabutyl)benzene, H2emi = N,N′‐ethylenebis(2‐mercaptoisobutyramide], have been synthesized and fully characterized as models of the active site of[NiFe] hydrogenases. The three‐dimensional structure of [Ni(xbsms)Ru(p‐cymene)Cl]+ reveals a nickel center in a square‐planar dithioether‐dithiolate environment that is connected to a ruthenium moiety via a Ni(μ‐SR)2Ru bridge. These complexes catalyze hydrogen evolution by electroreduction of the weakly acidic Et3NH+ ions in dimethylformamide and are therefore among the first bio‐inspired functional models of [NiFe] hydrogenases. The catalytic activity of these new complexes is explained by the existence of a cooperative effect between the metal centers and is further related to their electronic properties. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.200700067